Copolymeric siloxanes



A. J. BARRY ETAL coPoLYMERIc sILoxANEs Jan. 24, 1950 Filed July 31,- 1948 Vl 8 D r H J L .R 0MM ...ma om l .l \Y o n w 1% b P um: w3 .l0 F. l VW 8 5 a s |o w @Y w i L ,L 1 IQ @L Humm wml@ L m m ,E S S lm R Hw r\ llw M n In .m T |lo z o c\ \\`A l \A Nm 0 0 D D o.. 5 0 5 0 o 0 oO 7. 6 5 4 3 2 .M m m M m M JOHN I4. lt/(Ey A 'ITRNE Y Patented Jan. 24, 1950 COPOLYMERIC SILOXANES Arthur J. Barry and John W. Gilkey, Midland,

Mich., Midland, Mich.,

assignors to Dow Corning Corporation,

a corporation of Michigan Application July 31, 1948, Serial No. 41,823 5 Claims. (Cl. Zim-448.2)

This invention relates to new compositions of matter comprising linear copolymeric siloxanes f vthe type RaSiOlCaHsCI-IsSiOlaSlRs.

Copolymeric siloxanes of the type (CH3) aSiOHCHsMSiOlnSMCHa):

are known to the art. These materials are stable fluids possessing good temperature-viscosity behavior which renders them eminently adaptable for use as lubricants and damping media. However, the dimethylsiloxane trimethylsiloxane copolymeric iluids have freezing points in the neighborhood of 75 C. This limitation renders particularly the high polymers, unsuitable for use in the extreme temperatures encountered at high altitudes and in the Arctic.

It is an object of this invention to provide materials which possess good stability and temperature-viscosity behavior and at the same time, have freezing points below 120 C. Another object of this invention is to provide lubricants and damping media suitable for use on aircraft under any conditions encountered in nature. Other objects and advantages will be apparent from the following description.

This invention relates to copolymeric siloxanes of the type (CH3) zRSO (CaHsCHaSiO) nSiR(CH3) 2 where n has a positive value and R is a methyl or ethyl radical. These compounds may be in the form of distillable low molecular weight products in which n is an integer from 1 to 4 inclusive, or in the form of non-distillable polymeric mixtures in which n has an average value greater than four.

These copolymers may be prepared from hydrolyzable silanes of the type (CHs)3SiX, C2H5(CH3)2SiX and CHaCzHsSiXz where X is a halogen or alkoxy. Such silanes may be produced by any appropriate method. For example, they may be synthesized by the well known Grlgnard reaction. Alternatively, the ethylmethylsilanes may be prepared by reacting CHaHSiClz with ethylene under pressure to give CHsCzHsSiCla.

This method is more fully disclosed in the copending application of Arthur J. Barry et al, Serial Number 674,926, led June 6, 1946, assigned to the Dow Chemical Company.

The hydrolysis of the silanes to give the copolymers of this invention may be carried out in two ways. The trlorgano silane and the ethylmethylsilane may be mixed and cohydrolyzed and cocondensed by any of the methods known to the art. In such a process the reaction may be carried out either with or without a catalyst and in the presence or absence of a solvent. It is preferred that the hydrolysis and condensation be carried out at temperatures between 0 C. and 250 C. The triorganosilane and the ethylmethylsilane may be hydrolyzed separately and the hexaorganosiloxane and the ethylmethylsiloxane so obtained, which may be completely condensed, may be mixed and copolymerized by vcontacting them with an interaction catalyst such as a strong acid or an alkali metal hydroxide. In this method it is preferred that the temperature employed be between and 200 C. A solvent may be used if desired.

The copolymers of this invention are linear in structure, and the molecules are composed of ethylmethylsiloxane chains end-blocked with trimethyl or ethyldimethyl silyl units. The lower members of both the homologous series may be separated from the reaction mixture by distillation.

The viscosity ol the products obtained by cocondensing or interacting the triorganosilanes and the ethylmethylsilanes is readily controlled by regulating the molar ratio of triorgano to diorgano constituents. When the molar ratio of triorgano to diorgano silanes is high the viscosity of the copolymer product will be low. When this molar ratio is low the viscosity of the product will be high. Thus, it is possible to obtain copolymers of any desired viscosity.

The trimethylsiloxane ethylmethylsiloxane and ethyldimethylsiloxane-ethylmethylsiloxane copolymers of this invention possess a combination of low freezing points and relatively small change in viscosity with temperature which renders them highly useful as low temperature lubricants and damping media. This combination of properties is both advantageous and unexpected.

As a, comparison of the temperature-viscosity slopes of some trimethylsiloxane-ethylmethyl siloxane copolymers with trimethylsiloxanedimethylsiloxane copolymers, recourse may be had to the accompanying drawing. The drawing is a graph of the kinematic viscosity in cen tistokes against the temperature in degrees F. on an ASTM standard viscosity-temperature chart. The viscosity-temperature slopes of various trimethyl end-blocked ethylmethylsiloxanes are shown by lines AB, CD, and IJ, while the viscosity-temperature slopes oi' corresponding trimethyl end-blocked dimethylsiloxanes are shown by lines EF, GH and KL. It can be seen that the slopes of the copolymers of this invention are equal to or superior to those of the dimethylcopolymers. A comparison of the freezing points of the present copolymers with trimethylsiloxanedimethylsiloxane copolymers is shown in Table I.

From the data given in this table it is readily seen that the copolymers of this invention extend the useful range of lubricants and damping media. by more than 40 C., without loss of desirable temperature-viscosity properties.

For a better understanding of this invention, the following examples, which should be considered as illustrative only, are given.

EXAMPLES Example 1 357 g. of C2H5CIhSiClz and 868 g. of (CH3)3SiCl were combined and 885 g. of H2O was added slowly thereto with stirring. During the addition, the temperature was maintained below 20 C. by external cooling. This mixture was reuxed for 2 hours at 110 C. whereupon an acid layer and a product layer were formed. The acid layer was removed and the product layer was diluted with an equal volume of 5% NaOH. This mixture was heated for 2 hours at 88 C.. with agitation, after which the heat was removed and agitation was continued for an additional two hours. Residual NaOH was then removed. The fluid product was washed with H2O until neutral, dried, and filtered. The filtered product was then fractionally distilled and the following compounds were obtained in the percentages indicated: (CH3) 3SiOC2H5CH3SiOSi(CH3 a, 46.7%;

(CH3) 3SiO C2H5CH3S1O] zSi (CH3) 3, 26.5 (CH3) BSO [czHsClhSOlsSi (CI-h) s, 11.0

and a residue of (CH3) :SiOlCzHCHsSiOlISHCI-la) 3, 15.8

Emample 2 This example illustrates the preparation of trlmethyl end-blocked linear ethyl methyl siloxanes from mixed ethyl methyl cyclic siloxanes and (CHiisSOSMCI-Iala. 618 g. of mixed cyclic ethyl methyl siloxanes having the formula [C2H5CH3S1O1:

were combined with 1376 g. of

(CH3)3SiOSi(CI-h)3,

and 200 g. of concentrated HzSOi were added slowly to the mixture with stirring. During the addition, the temperature did not rise above 30 C. After addition of the HzSOi. the mixture was agitated for two hours at room temperature. An acid layer and a product layer formed and were separated. The product layer was washed until neutral. dried over CaCl2, and iltered. The ltered liquid was then fractionally distilled and the following products were isolated in the proportions indicated:

(CH3) 3SOC2H5CH3SOS1 (CH3 3, 43.5

and

(CH3) @SiOiCzHsCI-IaSiOlISi (CH3 s residue 29.0%.

Representative trimethyl end-blocked ethylmethyl-siloxanes prepared and isolated as shown in examples one and two are listed in the Table II.

Example 3 Ethyldirnethyl end-*blocked ethylmethylsiloxanes were prepared according to the method shown in Example 1 by cohydrolyzing ethyldimethylchlorosilane and ethylmethyldichlorosilane. The properties of some of the copolymers of this series are given in Table III.

Table I Freezing Point. C.

Total Number Silicon Atoms Freezing Point, C.

Freezing Point, C.

Table III Boiling Refractive S o Compound .,Pin dex, Prizn ravit mn,... N' 20 [(CHz) 10111551120 152 l. 40m 1m 798 CHt (CHa)2CzH5SiO lSiCzHKCHa): 212 1.4075 below -120 .850

CH: (CH3)1C1H5SO[(S}1(E)I ]SC1H|(OHI) 259 1.4121 belw 1w .880

CH3 (0Hx)1CzH|SiO[ai?I ]SiC|H5(CHa)I 301 1.4150 below -lm .901

' CHS (CH|)lCaH|SiO[SiO ]SiCxH|(CH|)a 364 1.4210 below 12) CzHs 4 That which is claimed is: 4. 1.

CH; (CHz)aS10[SiO :l SKCH:

where n has a positive value.

CH3 (CHs)aSiO[SiO :l 81(0110):

CIB: n

where n is an integer from 1 to 4 inclusive.

where n has a. positive value.

20 where n is en integer from 1 to 4 inclusive.

ARTHUR J. BARRY. JOHN w. GILKEY.

No references cited.

Certificate of Correction Patent No. 2,495,362 January 24, 1950 ARTHUR J. BARRY ET AL.

It is hereby certied that errors appear in the printed specification of the above numbered patent requiring correction es follows:

Column 5, Table III, for that portion of the third compound reading on. on, [sie read sie OIHI C|H| i line 21, for that portion of the formulaJ reading Si(CHg), read S'i(O'H,),;

and that the said Letters Patent should be read with these corrections therein that the Berne may conform to the record of the ease in the Patent Ofliee.

Slgned and sealed this 28rd day of May, A. D. 19450.

THOMAS F. MURPHY,

Aniston! Uommuanet of Patmta. 

